Metal-containing compounds of nicotine fluosilicate as lousicide



Patented Mar. 14, 1 95! METAL-CON TAININ G COMPOUNDS OF NICO- TINE FLUOSILICATE AS LOUSICIDE Ernest F. Waller, Burlington, Vt., George L. Walker, Durham, N. H., and James F. Adams,

Wilmington, DeL, assignors to Allied Chemical & Dye Corporation, a corporation of New'York No Drawing. Application January 10, 1946, Serial No. 640,376

Claims. 1

This application is a continuation in part of our U. S. application Serial No. 585,314 filed March 30, 1945, which has become abandoned.

The invention relates to a new insecticide for the control of livestock and poultry lice and to a process of using the lousicide to effect such control.

Three known methods for controlling lice infesting farm animals, particularly livestock, are to subject the livestock to a dusting, spraying or a Wet dipping treatment with insecticides. Among the insecticides commonly used for spraying or dipping are: wettable rotenone, sodium arsenite, lime sulfur, nicotine sulfate and coal tar and petroleum distillates; for dusting, rotenone and sulfur, pyrethrum and sulfur and sodium fluoride and sulfur are used. While these methods, if correctly applied, destroy the majority of adult parasites, they do not destroy the eggs, nor are they eifective enough for a sufiiciently long period, say days, to kill the young parasites as they are hatched.

It is an object of this invention to provide a novel insecticide which is eiiective for the control of livestock and chicken lice and Which retains its efiectiveness for a relatively long period of time, of the order of 20 days or longer, after application to the animal. Another object is to provide such insecticide which can be effectively applied by the well-known dusting and wet dipping methods.

We have found that the nicotine fiuosilicates of certain metals in period 3 in the periodic table of elements, i. e., zinc, copper, nickel and cobalt, preferably mixed with markably eiTective lousicides and retain their effectiveness for relatively long periods of time, say, of the order of 20 days or longer, so that animals treated therewith remain substantially free of lice for such relatively long periods. Of the nicotine fluosilicates mentioned, the zinccompound is preferred.

The amount of zinc, copper, nickel or cobalt nicotine fiuosilicate mixed with the wettable sulfur may vary from about 4 to about 7 parts by Weight of metal nicotine fluosilicate to from about 20 to about 96 parts by weight of wettable sulfur. To this mixture may be added up to 75 parts by weight of filler or diluent, hereinafter referred to as a carrier, such as pyrophyllite, talc, kaolin, gypsum or starch. When the insecticidal mixture is used without a carrier, to avoid possible injury to the host the amount of wettable sulfur should be within the upper limits wettable sulfur, are reof the range above given so that the mixture A preferred formula for the lousicides of this invention is:

Pe cent Zinc nicotine fiuosilicate 6.- 5 Wettable sulfur 25.0 Filler such as pyrophyllite 68:5

The zinc nicotine fiuosilicate has a zinc fluosilicate to chemically combined nicotine mol ratio within the limits of 1:1 to 111.5. Such compounds may be prepared by reacting commercial nicotine containing 5% to 10% water with zinc .fiuosilicate in the presence of a polar solvent such as water, the lower aliphatic alcohols, particularly the aliphatic monohydric alcohols having less than 6 carbon atoms, or any mixture of these solvents, heating the reaction mixture at a temperature within the range of room temperature to 110 C'., the decomposition temperature of zinc fiuosilicate, and isolating the vzinc nicotine fiuosilicate by evaporating off the solvent under conditions, for example, vacuum, so as to avoid decomposition of the zinc nicotine fiuosilicate. For the preparation of preferred zinc nicotine fluosilicate having ,a zinc fiuosilicate to nicotine mol ratio of 1:1, commercial nicotine is added to methanol containing 5% to 10% water, in which the zinc iiuosilicate is dissolved, the reaction being preferably carried out at room temperature, e. g. 25 C. If desired, however, the reaction temperature maybe maintained within the range of 0 to 0., the pressure being such as to prevent any substantial evaporation of the solvent employed. Under these conditions most of the zinc nicotine fluosilicate precipitates.

Copper nicotine ffuosilicates, usedin the production of the lousicide of this invention, have a copper fiuosilicate to chemically combined nicotine mol ratio within the range of from 1:1 to 1:4; the preferred compounds have .a copper fluosilicate to nicotine mol ratio of from 1:2 to 1:4. The metal nicotine fluosilicates may or ,not

contain water of crystallization.

The copper nicotine fiuosilicates maybe preparedbyreacting copper fluosilicate and nicotine in the presence of a polar solvent such as water, the lower aliphatic alcohols, particularly the aliphatic monohydric alcohols having less than 6 carbon atoms, or any mixture of these solvents at a temperature within the range of from room temperature (25 C.) to about 140 C., preferably within the range of 35 to 60 C. For example, commercial nicotine containing about water may be reacted with copper fiuosilicate (CllSlFc.4I-I20) in the presence of water as the solvent by heating the reaction mixture at about 60 C. to produce a reaction mass containing copper nicotine fiuosilicate and water, and the copper nicotine fluosilicate recovered from the reaction mass by evaporating off the solvent under any condition, e. g. reduced pressure, below the decomposition temperature (140 C.) of the copper nicotine fluosilicate. Depend-- ing upon the ratio of copper fluosilicate to nicotine, copper products may be thus produced having a copper fluosilicate to nicotine mol ratio within the limits of 1:1 to 1:4. The nickel and cobalt nicotine fluosilicates may be prepared by substantially the same procedure as outlined above in connection with the copper compound.

The wettable sulfur improves the sticking or adhering properties of the zinc nicotine fluosilicate; in addition, the incorporation of the wettable sulfur results in a lousicide having unexpectedly greater toxic properties than the sum total of the toxic properties of the individual constituents. The wettable sulfur may be prepared by mixing with extremely finely divided sulfur about i% b weight of a mixture of about equal parts of a conditioner, such as clay, and of a wetting agent such as Saponine, a sodium salt of alkyl aryl sulfonate.

The following tests illustrate the effectiveness of my invention:

Test 1 A pen of 23 hens heavily infested with Menopon biseriatum was treated by dusting a mixture of 6.5% by weight of zinc nicotine fluosilicate, 25.0% wettable sulfur and 68.5% pyrophyllite into the feathers of the birds. By the time the last birds were dusted, no active lice could be found on some of the first birds treated. The birds were caught and examined after 24 hours and on the 8th, 15th, 22nd and 29th days after the dusting. No lice were found on all the birds in the first two examinations and only three lice were found on one bird in the examination on the 15th day. This bird was retreated and was found negative along with the remainder of the flock in the examinations made on the 22nd and 29th days.

Test 2 In this test a pen of 21 hens and 4 cockerels, which was heavily infested with lice, were dusted with level teaspoon per bird of the mixture used in the first test. The mixture was placed in the feathers and the feathers ruffled with the hands to make ,sure that the dust reached the skin. A second pen of 26 birds was empty, it being evident that the dust had remained on the birds long enough to kill the lice as they were hatched.

Test 3 A flock of 9'7 hens confined in a chicken house were treated with 1 gram per hen of a mixture containing 5.0% by weight Zinc nicotine fiuosilicate and 95.0% pyrophyllite. The nesting areas were also dusted. Inspection of the hens on the 1st, 3rd, 13th, 20th and 28th days following treat ment showed complete control, i. e. no lice were found. The same results were obtained using a like amount of a mixture consisting of 5.0% by weight zinc nicotine fluosilicate, 40.0% wettable sulfur, and 55.0% pyrophyllite.

A flock of 23 heavily infested hens were dusted with 75 grams of a mixture consisting of 6.5% zinc nicotine fiuosilicate, 25.0% wettable sulfur and 68.5% pyrophyllite. 25 grams of this mixture were dusted over the nesting areas used by the flock. 12 days after this treatment inspection of the flock showed only one hen slightly infested, the remaining 22 being completely free of lice.

Test 4 Two flocks of heavily infested chickens were treated with the mixture used in the preceding test. One flock of 24 chickens was dusted with this mixture, each chicken receiving 1 level teaspoon of mixture. The other flock of 26 chickens received between 1%; to 2 level teaspoons of mixture per chicken. Observations made 2, 8 and 25 days after the application of the mixture to both flocks showed all chickens of both flocks to be free of lice.

Test 5 A flock of 40 hens heavily infested with lice were divided into five groups of 8 hens each and two of these groups of hens treated individually with approximately teaspoonful of the following insecticidal compositions:

A.-2.2% zinc nicotine fluosilicate, 25% wettable sulfur and 72.8% carrier (chiefly pyrophyllite) B.-3.l% copper nicotine fiuosilicate, 25% wettable sulfur and 71.9% carrier (chiefly pyrophyllite).

For comparative purposes, three recognized com mercial products commonly used as lousicides were applied to the other 3 groups of 8 hens each. One product (hereinafter referred to as product C) contained .5% rotenone, 5.5% orthophenylphenol, 13% sulfur and the remainder inert ingredients. Another product tested for comparative purposes (hereinafter referred to as product D) contained 29.25% sodium fluoride, 20% sulfur, .5% nicotine, 15% sodium chloride, .6% sodium sulfate, and the remainder being inert material (chiefly tobacco fiber) and the last product tested for comparative purposes (hereinafter referred to as product E) contained 7% orthohydroxybiphenyl, 5% petroleum oil, the remainder being inert material (chiefly extracted pyrethrum) 2 days after the treatment, all 8 hens treated with product B were found to be free of lice. 7 of the hens treated with product A were found to be free of lice. Of the hens treated with products C, D and E, 3 treated with product C, only 1 treated with product D and 2 treated with product E were found to be free of lice. This test shows the marked superiority as a lousicide of the products of this invention as compared with known products, hereinabove identified.

Test 6 In a test against cattle using a mixture containing 7.5% zinc nicotine fiuosilicate, 87.5% wettable sulfur and 5.0% pyrophyllite, 3 heavily infested dairy heifers standing in 3rd, 4th and 5th place in a string of were dusted with the mixture using a hand powered dusting machine and applying the dust over the entire body except the face. Combings from these 3 animals were examined at the end of 24 hours and only a few living but very sluggish nymphs were found. Combings were again collected and examined under a microscope on the 9th day after the test and no living lice or nymphs were found.

Test 7 In another test carried out in the same manner using the same mixture on 3 mature cows heavily infested with both biting and sucking lice, combings were examined after 48 hours and only an occasional biting louse was found. No large sucking lice were observed. Combings were obtained from these animals and examined at the end of the week and no biting or sucking lice were found.

Test 8 In another series of tests against dairy cattle heavily infested with biting lice (Trichodectes scalaris), mixtures containing (1) 5.0% zinc nicotine fluosillcate, 40.0% wettable sulfur, 55.0% inert carrier (pyrophyllite), (2) 10.0% zinc nic otine fluosilicate, 40.0% wettable sulfur and 50% inert carrier (pyrophyllite), and (3) 10.0% zinc nicotine fluosilicate and 90.0% inert carrier pyrophyllite), were used. The tested animals were found completely free of lice 21 days after treatment with these mixtures.

Test 9 A test was carried out on pigs which were found to harbor numerous Haematopinus suis using the same mixture as in the test against cattle. The removal and destruction of the lice was rapid and complete; however, the hard dry skin of the pig together with its sparse hair resulted in little of the powder adhering to the skin so that the young were not destroyed as they were hatched, as was the case in the tests against cattle.

The lousicide of this invention may be applied to the animal in dry form, as by dusting it over the skin or hide of the animal as in the above tests, or sprayed dispersed in an aqueous or other medium over the animal, or applied to the animal by the well-known dipping method. For example, an aqueous suspension of the mixture may be provided in a tank or trough and the animal dipped or caused to pass through the suspension so that it is applied to its hide, skin or feathers. For thus applying the mixture, from 6 to 8 ounces of mixture per 10 gallons of water may be used. The preferred formula for use as a dip or spray in an aqueous medium is: 8 ounces of the mixture to 10 gallons of water.

In the foregoing tests the zinc nicotine fluoand wettable sulfur in silicate used had a zinc fluosilicate to nicotine mol ratio of one to approximately one, and the copper nicotine fiuosilicate had a copper fluosilicate to nicotine mol ratio of one to approximately two.

The references to metal fiuosilicate to nicotine ratios in the specification are to mol ratios.

Since certain changes may be made in the above product and different embodiments of the invention could be made without departing from the scope thereof, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A composition suitable for use as a lousicide comprising a nicotine fluosilicate of a metal in period 3 of the Periodic Table of elements of the group consisting of zinc, copper, nickel and cobelt, and wettable sulfur.

2. A composition suitable for use as a lousicide comprising zinc nicotine fluosilicate and wettable sulfur.

3. A composition suitable for use as a lousicide comprisin zinc nicotine fiuosilicate having a zinc fiuosilicate to nicotine mol ratio of 1:1 to 1:1.5 proportions of 4 to 7 parts by weight of zinc nicotine fiuosilicate to 20 to 96 parts by weight of wettable sulfur.

4. A composition suitable for use as a lousicide comprising zinc nicotine fluosilicate having a zinc fiuosilicate to nicotine mol ratio of 1:1 to 1:15, wettable sulfur in proportions of 4 to 7 parts by weight of zinc nicotine fiuosilicate to 20 to 96 parts by weight of wettable sulfur, and a carrier in amount not exceeding parts by weight.

5. A composition suitable for use as a lousicide comprising copper nicotine fluosllicate having a copper fluosilicate to nicotine mol ratio of from 1 1 to 1 :4 and wettable sulfur.

ERNEST F. WALLER. GEORGE L. WALKER.

JAMES F. ADAMS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A COMPOSITION SUITABLE FOR USE AS A LOUSICIDE COMPRISING A NICOTINE FLUOSILICATE OF A METAL IN PERIOD 3 OF THE PERIODIC TABLE OF ELEMENTS OF THE GROUP CONSISTING OF ZINC, COPPER, NICKEL AND COBALT, AND WETTABLE SULFUR. 